Beam-foil lifetimes of highly ionized silicon

Electronically excited states of Si ions are created by passing a 20 MeV Si⁵⁺ beam through a thin carbon foil. The EUV-radiation (λ=13–61 nm) emitted by the beam is analyzed using a grazing-incidence spectrometer. From the decay curves, lifetimes of 24 low lying levels in Si VIII to Si XII and of the 4f and 5g levels of Si XI and Si XII are derived. Cascades from doubly excited states turn out to be an important contribution to the radiation observed. The lifetime values of this work are compared to theoretical data mainly of Wiese, Sinanoλu and Dankwort/Trefftz. Most experimental values agree with at least one of the theoretical values. The decay time 560 ps of the 2s2p ^{3 3} D ₃ ⁰ state of Si IX is clearly longer than the theoretical prediction (highest value 455 ps by Sinanoglu).     

Mimicking primary processes in photosynthesis—covalently linked porphyrin quinones

Porphyrin quinones (P-Qs), covalently linked via different aliphatic bridges, have been synthesized and studies in their (porphyrin) cationic and (semiquinone) anionic radical states by EPR, ENDOR and TRIPLE resonance techniques. Electron transfer (ET) from the porphyrin donor to the quinone acceptor could be observed by time-resolved picosecond fluorescence spectroscopy (singlet ET) and by time-resolved EPR spectroscopy (triplet ET) in isotropic fluid solution and in anisotropic media (liquid crystals and reversed micelles). Steady-state in situ photoexcitation of P-Qs in CTAB cationic reversed micelles yielded the corresponding semiquinone radical anions. In TRITON X-100 reversed micelles both the radical cation of the porphyrin and the radical anion of the semiquinone could be detected, which occured in complete emission. In covalently linked porphyrin flavins ET from the photoexcited porphyrin fragment to the flavin and, in addition, energy transfer from the photoexcited flavin to the porphyrin could be observed.     

Low-temperature specific heat of the cluster compound Au55 (P(C6H5)3)12Cl6

Specific-heat measurements on the cluster compound Au₅₅(P(C₆H₅)₃)₁₂Cl₆ at temperatures 0.06 K ≤T≤3 K and in magnetic fields 0≤B≤6 T are reported. While above 0.6 K the specific heatC is dominated by the inter-cluster vibrational contribution observed previously, an anomalous increase ofC towards lowT is observed below 0.3 K, withC ～T ^?2. This contribution develops into a Schottky-like anomaly forB≥0.4 T, indicating that it might be attributed to local moments which are also observed in ESR measurements. From the height of the anomaly one can infer that approximately one tenth of the Au₅₅ clusters carry a magnetic moment. For 0.6 K≤T≤1 K andB=0 our data indicate the absence of a linear electronic specific-heat contribution expected for bulk Au. This possibly constitutes the first direct observation of the quantum-size effect on electronic energy levels in the specific heat.     

The aromatic diboracyclopropenyl (diboriranyl) anion; CB2H3 −: An ab initio study

The most stable structure of CB₂H₃ ^–, as established computationally, is the aromatic diboracyclopropenyl (diboriranyl) anion (5), while open-chainC _2v, isomer H₂BCBH (7) is only 3 kcal/mol higher in energy at the QCISD(T)/6-311 +G^**//MP2/6-31+G^*+ZPE (HF/6-31 +G^*). The 47-kcal/mol barrier between cyclic,5, and open-chain,7, structures suggests that both of them may be observed. The aromatic stabilization energy of the diboriranyl anion (18 kcal/mol) is half the value in the isoelectronic cyclopropenium ion, C₃H₃ ⁺. The computed, by IGLO method (5a), and experimental (6a) chemical shifts,(¹³C) and(¹¹B), agree within 4 ppm range. The theoretical vibrational frequencies of the most stable isomers,5 and7, are presented for experimental verification of these species.     

Synthesis of annelated derivatives of tetrafluoro-10<Emphasis Type="Italic">H</Emphasis>-imidazo[1,2-<Emphasis Type="Italic">b</Emphasis>][1,2]benzooxazin-10-one and 2-pentafluorophenylpyrazine 1,4-dioxide by condensation of alicyclic 2-hydroxyamino oximes with pentafluorophenylglyoxal

Reactions of alicyclic 2-hydroxyamino oximes with pentafluorophenylglyoxal afford mixtures of annelated derivatives of 2-pentafluorophenylpyrazine 1,4-dioxide and tetrafluoro- 10H-imidazo[1,2-b][1,2]benzooxazin-10-one. The structures of the latter were established by X-ray diffraction analysis.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1636–1639, August, 2004.     

Copper(II) interaction with unstructured prion domain outside the octarepeat region: speciation, stability, and binding details of copper(II) complexes with PrP106-126 peptides

Copper(II) complexes of the neurotoxic peptide fragments of human and chicken prion proteins were studied by potentiometric, UV-vis, CD, and EPR spectroscopic and ESI-MS methods. The peptides included the terminally blocked native and scrambled sequences of HuPrP106-126 (HuPrPAc106-126NH2 and ScrHuPrPAc106-126NH2) and also the nona- and tetrapeptide fragments of both the human and chicken prion proteins (HuPrPAc106-114NH2, ChPrPAc119-127NH2, HuPrPAc109-112NH2, and ChPrPAc122-125NH2). The histidyl imidazole-N donor atoms were found to be the major copper(II) binding sites of all peptides; 3N and 4N complexes containing additional 2 and 3 deprotonated amide-N donors, respectively, are the major species in the physiological pH range. The complex formation processes for nona- and tetrapeptides are very similar, supporting the fact that successive deprotonation and metal ion coordination of amide functions go toward the N-termini in the form of joined six- and five-membered chelates. As a consequence, the peptide sequences investigated here, related to the neurotoxic region of the human PrP106-126 sequence, show a higher metal-binding affinity than the octarepeat fragments. In the case of the HuPrP peptide sequences, a weak pH-dependent binding of the Met109 residue was also detected in the 3N-coordinated complexes.     

The UV photolysis (λ = 185 nm) of liquid t-butyl methyl ether

t-Butyl methyl ether has been UV photolysed (λ = 185 nm) to a maximal conversion of less than 0·1%. A study of the products (quantum yields) has been made: methanol (0·40₅), t-butanol (0·20), isobutene (0·17₈), t-butyl neopentyl ether (0·14₂), t-butyl ethyl ether (0·13₄), 1,2-di-t-butoxyethane (0·097), methane (0·056), isobutane (0·046), isopropenyl methyl ether (0·030), hydrogen (0·020), neopentane (0·016), ethane (0·015), formaldehyde (0·012), 2-methoxy-2-methyl-4-t-butoxybutane (0·005), hexamethylethane (0·0048), 2-methoxy-2-methylbutane (0·0027), 2-methoxy-2-methyl-3-t-butoxypropane (0·002), isopropyl methyl ether (0·0015), formaldehyde t-butyl methyl acetal (0·001), formaldehyde di-t-butyl acetal (0·001), 2-methoxy-2-methyl-4,4-dimethylpentane (0-001), 2-methoxy-2-methyl-3,3-dimethylbutane (0·0003), 2,5-dimethoxy-2,5-dimethylhexane (0·0002), di-t-butyl ether (5 · 10^?5), 2,2-dimethyloxirane (?, <- 0·001). There is no decomposition of the t-BuO radical into acetone (< 5 · 10^?4) and CH₃. Cyclisation reactions leading to α,α-dimethyloxetane (< 10^?4) and 1-methoxy-1-methylcyclopropane (< 10^?4) do not occur. The material balance yields C₅H_11·97O_1·018.The main modes of fragmentation (ca 82%) are represented by the homolytic CO bond split, either into t-butyl and methoxy (ca 52%) or into t-butoxy and methyl (ca 30%), Fragmentation into methanol and isobutene (8·5%) as well as into formaldehyde and isobutane (2%) are further modes of decomposition. The break of a CC linkage (4·5%) mainly occurs by elimination of molecular methane. A CH bond split has a probability of ca 3% with the methoxy CH bond the more likely one to break.     

Sampling procedure and a radio-indicator study of mercury determination in whole blood by using an AMA 254 atomic absorption spectrometer

A sampling procedure appropriate for the determination of mercury in whole blood was tested by using both inactive controls and a ¹⁹⁷Hg mercury radio-indicator. To exclude the influence of the instrumental device (an AMA 254 single-purpose mercury atomic absorption spectrometer) on the determination of mercury in whole blood, the function of the instrument was checked by using rat blood with metabolised ¹⁹⁷Hg. The measurement procedure was found to be free of errors. However, the study showed that the material used for the sampling vessels is a crucial parameter for obtaining accurate analytical results. The stability of solutions and samples was tested towards polyethylene (PE) and polypropylene (PP) vessels. PE displayed a time-dependent increase in the mercury content both in the samples and in the blood control material. The probable cause of this increase was direct contamination from the material of the vessel and/or diffusion of mercury from the environment through the vessel walls related to a strong complexing affinity of the sample matrix. This assumption was confirmed by supplying the vessels with the complexing agent Na₂EDTA (0.05 mol L^–1). Commercial PP vessels for blood sampling (Sarstedt S-Monovette Metall Analytik) did not give rise to statistically significant variations in mercury content in the samples and blood control material over a 30-day period.     

Environmental effects on a prion's helix II domain: copper(II) and membrane interactions with PrP180-193 and its analogues

An abnormal interaction between copper and the prion protein is believed to play a pivotal role in the pathogenesis of prion diseases. Copper binding has been mainly attributed to the N-terminal domain of the prion protein, but this hypothesis has recently been challenged in some papers which suggest that the C-terminal domain might also compete for metal anchoring. In particular, the segment corresponding to the helix II region of the prion protein, namely PrP180-193, has been shown both to bind copper and to exhibit a copper-enhanced cytotoxicity, as well as to interact with artificial membranes. The present work is aimed at extending these results by choosing the most representative model of this domain and by determining its copper affinity. With this aim, the different role played by the electrostatic properties of the C- and N-termini of PrP180-193 (VNITIKQHTVTTTT) in determining its conformational behaviour, copper coordination and ability to perturb model membranes was investigated. Owing to the low solubility of PrP180-193, its copper affinity was evaluated by using the shorter PrPAc184-188NH2 (IKQHT) analogue as a model. ESI-MS, ESR, UV/Vis, and CD measurements were carried out on the copper(II)/PrPAc184-188NH2 and copper(II)/PrP180-193NH2 systems, and showed that PrPAc184-188NH2 is a reliable model for the metal interaction with the helix II domain. The affinity of copper(II) for the helix II fragment is higher than that for the octarepeat and PrP106-126 peptides. Finally, the different ability of PrP180-193 analogues to perturb the DPPC model membrane was assessed by DSC measurements. The possible biological consequences of these findings are also discussed briefly.     

Optimization of time resolution and detection limit for online measurements of 222Rn in water

The online measurements of radon in flowing water with high temporal resolution and a lower limit of detection of some Bq/l is of growing interest in environmental research and earth sciences. Promising new fields of application in hydrogeology are the study of exchange and mixing processes and the monitoring of pumping procedures before and during groundwater sampling. A suitable, simple method has been proposed by Surbeck based on the separation of air and water by a diffusion membrane. Process parameters influencing the temporal resolution as well as the radon detection efficiency have been studied. Considering these results a new instrument has been developed enabling online radon-in-water measurement with time resolution of about one minute.